Expandable composition, blowing agent, and process for extruded thermoplastic foams

ABSTRACT

An extruded thin sheet foam is disclosed prepared from a polyolefin resin in which the blowing agent comprises a blend of from about 1 to 25% by weight of carbon dioxide and the balance of C3 to C4 VOCs. Thin foam sheets produced with the blowing agent age about twice as fast as foams prepared with VOCs, are remarkably stable, and can be produced at high throughputs.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a divisional application of U.S. applicationSer. No. 09/748,931, filed Dec. 27, 2000, which is hereby incorporatedherein in its entirety by reference.

FIELD OF THE INVENTION

[0002] This invention relates to an expandable composition and blowingagent for producing low density thermoplastic foams and a process forproducing an expanded thermoplastic foam product of low density using anexpandable thermoplastic composition. In particular, this inventionrelates to use of a blended blowing agent for incorporating into aplasticized thermoplastic resin for foaming by extrusion.

BACKGROUND OF THE INVENTION

[0003] Thermoplastic foam products can be produced by a wide variety ofprocesses, of which extrusion is but one, that are in part responsiblefor the wide variety of foam products available today. Foams range inconsistency from rigid materials suitable for structural use to flexiblesubstances for soft cushions and packaging materials. These foams rangein cellular formation from open or interconnecting-cell foams to closedor unicell foams. The cell structure may range from large to fine.Electrical, thermal, mechanical, and chemical properties can be variedwithin wide limits depending on the thermoplastic resin composition andthe method chosen to create the foam. Foamed thermoplastics range indensity anywhere from about 10 kg/m³ to over 1,000 kg/m³, although thelatter perhaps more properly are called microcellular structures. Truefoams are considered to have a density of less than about 800 kg/m³.

[0004] Many methods have been developed for the manufacture of foamedthermoplastics, which generally can be classified into three groups: 1)methods for adding a gaseous “blowing agent” to the thermoplastic duringprocessing, 2) methods for producing a gaseous blowing agent in thethermoplastic during processing, and 3) methods for forming athermoplastic mass from granules to obtain a cellular structure. Similarblowing agents sometimes are used in the various methods to producefoams. However, the effectiveness of a particular blowing agent variesconsiderably depending on the thermoplastic resin composition, themethod chosen, the process conditions, the additives used, and theproduct sought.

[0005] Blowing agents work by expanding a thermoplastic resin to producea cellular thermoplastic structure having far less density than theresin from which the foam is made. Bubbles of gas form around“nucleation sites” and are expanded by heat or reduced pressure or by aprocess of chemical reaction in which a gas is evolved. A nucleationsite is a small particle or conglomerate of small particles thatpromotes the formation of a gas bubble in the resin. Additives may beincorporated into the resin to promote nucleation for a particularblowing agent and, consequently, a more uniform pore distribution.However, the foam is maintained by replacing the blowing agent in thecells with air. Diffusivity of the blowing agent out of the cellsrelative to air coming into the cells impacts the stability of the foamover time and whether the cells of the foam may collapse. Additives maybe incorporated into the resin and process conditions may be adjusted toassist in controlling the diffusivity of the blowing agent, to promotefoam stability, and to limit collapse of the foam to acceptable limits.

[0006] Methods for producing a blowing agent in situ usually involve achemical reaction that evolves gas. Polyethylene, silicone, epoxy, andvinyl foams have all been produced by adding a substance that willproduce a gaseous blowing agent chemically. For example, dinitrosocompounds and hydrazides, which evolve nitrogen gas on decomposition,and bicarbonates, which evolve carbon dioxide, have been added tothermoplastic resins to produce foams.

[0007] Polystyrene foams often are produced by “bead molding,” in whichpartially expanded granules or beads are heated in a mold in thepresence of a blowing agent to expand and fuse the particles into arigid unicellular structure. A volatile organic compound or some othergaseous blowing agent is impregnated into the beads. Heat is applied andthe pressure is released to cause the beads to expand and fuse.

[0008] There are several methods for adding a blowing agent to athermoplastic resin during processing to produce a foam.Ureaformaldehyde and polyvinylformaldehyde foams have been produced bywhipping air into a heated thermoplastic mass before it sets.Polyolefinic foams have been produced by introducing air or some othergas or volatile solvent into a heated thermoplastic polyolefin mass andthen heating the mass or reducing pressure to expand the gas and formpores of a desirable size. One more specific method is to impregnate athermoplastic resin with blowing agent under heat and pressure in aclosed vessel. The pressure is released to expand the blowing agent toform “prefoamed,” or partially expanded, beads. Prefoamed beads usuallyare further expanded in an enclosed vessel such as a mold to produce amolded foam product, such as is discussed hereinabove.

[0009] Another more specific method, to which the invention claimedherein relates, is to mix the blowing agent with molten resin underpressure and then extrude the mixture through a forming die into a zoneof reduced pressure. Shaped foams can be produced by extrusion foamingusing a forming die of particular configuration. Plank, which can be cutto a desirable shape, and thin foam sheets are produced in this manner.

[0010] Extrusion foaming is a continuous process in which a plasticizedthermoplastic resin is cooled and expanded when the resin and blowingagent are extruded into a zone of lower pressure. Mixing of blowingagent with polyethylene resin for extrusion foaming can take place in aslittle as few minutes or less because the resin is plasticized.Nucleating and stability control agents typically are used in extrusionfoaming to control cell formation, diffusivity of the blowing agent, andstability of the foam.

[0011] Many of the halogenated hydrocarbons have been used for severalyears as blowing agents in the various methods for producing foams fromthermoplastic resins. The halogenated hydrocarbons include thechlorofluorocarbons (“CFCs”) and hydrochlorofluorocarbons (“HCFCs”).CFCs and HCFCs are readily impregnable in thermoplastic resins and arereadily expandable under relatively mild conditions. CFCs and HCFCsgenerally produce foams of high quality with a minimum of processingdifficulty. The pore size is controllable, the foam has good stabilitywith minimum tendency to collapse after a period of time, and thesurface characteristics of the foam are smooth and desirable. Also,CFCs, HCFCs, and other halogenated hydrocarbons typically are either notflammable or are of low flammability, which greatly reduces the carewith which they may be used. These compounds have the further advantageof low toxicity. However, governmental regulation is phasing out use ofhalogenated hydrocarbons because the halogenated hydrocarbons may beresponsible for damage to the earth's ozone layer.

[0012] Producers of thermoplastic foam products have been seekingalternatives to CFC and HCFC blowing agents for a number of years toreduce or eliminate altogether the amount of halogenated hydrocarbonsused. A number of volatile organic compounds (VOCs) have been proposed,although many of these also are somewhat objectionable. VOCs include thelight aliphatic hydrocarbons such as propane, n-butane, isobutane,butylene, isobutene, pentane, neopentane, and hexane, to name but a few.The diffusivity of VOCs can be many times faster than that of thehalogenated hydrocarbons and harder to control. Foam collapse andstability problems have been encountered, although high quality foamscan be produced using VOCs. Many VOCs are highly soluble in polyolefinresins and may be difficult or time-consuming to remove. VOCs typicallyare flammable, thus presenting handling problems and safety concerns.

[0013] Inert gases have also been proposed as blowing agents, althoughthese sometimes do not provide acceptable results, especially forproducing extruded foams.

[0014] Inert gases include nitrogen, argon, xenon, krypton, helium, andcarbon dioxide. Nitrogen and carbon dioxide, in particular, have theadvantage of being inexpensive, readily available, and of not beingflammable, and are not considered to be harmful to the earth's ozonelayer. However, inert gases usually are not as readily soluble inthermoplastic resins as CFCs, HCFCs, and VOCs, are of higher volatility,and do not reduce the viscosity of the resin. Lubricants often are addedto the resin for extrusion foaming. The range of processing conditionsfor producing acceptable products is narrower than for CFCs, HCFCs, andVOCs. Mixing the resin with an inert blowing agent and keeping the inertblowing agent in the resin is more complicated than for CFCs, HCFCs, andVOCs. The surface texture of extruded foams sometimes is rough. Extrudedlow density foams and thick foams are difficult to achieve. The foamsometimes has poor stability and foam shrinkage can be uncontrollable.

[0015] Some blowing agent blends of VOCs and inert gases have beenproposed for use in preparing extruded polyolefin foams. For example,Ealding U.S. Pat. No. 3,839,238 discloses extruded polyolefin foamsprepared with a blowing agent system of a first blowing agent ofsaturated or unsaturated hydrocarbons and halogenated hydrocarbonsincluding, among others, pentane, hexane, heptane, and octane, and asecond blowing agent of carbon dioxide, nitrogen, air, methane, ethane,propane, and others. Foam density is disclosed as 0.05 to 0.5 g/cc (50to 500 kg/m³), which is a relatively high density.

[0016] Lee U.S. Pat. No. 5,348,984 discloses a blowing agent blend forcontinuously extruded polyolefin foams of about 25 to 75% by weightcarbon dioxide and about 75 to 25% hydrocarbon from the butanes andpropane. Foam density is from about 20 to 40 kilograms per cubic meter(0.02 to 0.04 g/cc).

[0017] Lee U.S. Pat. No. 5,462,974 discloses a blowing agent blend forcontinuously extruded polyolefin foams of about 20 to 80% by weightcarbon dioxide and about 80 to 20% hydrocarbon from the butanes andpropane. Foam density is from 20 to 100 kg/m³. Less carbon dioxide issaid to be useful if ethane is included in the blend.

[0018] The blowing agent blends of inert gas and VOC have been useful,but normally demand relatively slow extrusion rates.

[0019] Alternative blowing agents for extruded thermoplastic foams,processes for producing extruded foams using blowing agents, andthermoplastic resin compositions containing blowing agents are desirablethat provide improvements in the production and characteristics ofcontinuously extruded polyolefin foams.

SUMMARY OF THE INVENTION

[0020] The invention claimed herein relates to the use of a blowingagent for continuous extrusion foaming of thin sheets of relatively lowdensity polyolefin foams at relatively high extrusion throughputs,acceptable pore structure, and with short aging characteristics. Thisinvention is based on the recognition that initial foam dimensionalstability as the foam is produced at high throughput can be controlledby use of a particular blowing agent blend in which small amounts ofcarbon dioxide are incorporated into C-2, C-3, and C-4 VOCs. While notwishing to be bound by theory, it is believed that small amounts ofcarbon dioxide promote faster exchange of air with blowing agent. Inmany, but not all, instances, the foam initially collapses slightly andthen recovers at least about 95% of its as-extruded density. Foamsproduced in accordance with the invention are remarkably dimensionallystable, expanding and contracting less and aging about twice as fast asquality foams produced with VOC blowing agents not containing carbondioxide. These properties are significant in the aging of roll stock,reducing thickness variations in the machine direction of the foam thatcan result from tightness in the rolls as the aging foam expands, andreducing the hazards inherent in handling and processing flammable VOCs.

[0021] Extruded thin foam sheets of from about 0.01 to 0.5 inches thickand having a low density of from about 10 to 60 kilograms per cubicmeter can be produced by practice of the invention at extrusionthroughputs rates of from above about 100 kg/hr to 250 kg/hr.Throughputs of 200 kg/hr are typical, although the precise rate issomewhat machine dependent and not always readily quantifiable forgeneral application. Throughputs of 300, 400, and even 500 kg/hr shouldbe possible with larger extruders, which normally have not yet been usedfor thin sheets of extruded low density foams, but may be enabled by thepractice of the invention recited herein.

[0022] The foams expand and contract less than about 10 to 15% of theiroriginal as-extruded dimensions. Typically, these foams are aged forshipment within three days, normally achieving well less than 50% of thelowest explosive limit in air for the particular VOC used.

[0023] The blowing agent is a blended agent of carbon dioxide in anamount of from 1 to 25% by weight or less of the blowing agent. Thebalance is a hydrocarbon selected from among ethane, normal butane,isobutane, propane, or a mixture of any two or all of thesehydrocarbons. Carbon dioxide concentrations by weight of blowing agentof 10, 15, and 20% are useful in the practice of the invention.

[0024] In a more specific embodiment, extruded thin foam sheets of lowdensity polyethylene of nominal thickness of 0.05 to 0.150 inches and adensity of from 15 to 30 kg/m³ are produced at the rate of from about150 to 225 kg/m³ using a blowing agent of propane or one of the butanesor mixtures thereof blended with carbon dioxide in an amount of from 10to 20% by weight of the blowing agent. The foams are produced as rollstock and age as roll stock within 3 days to less than 30% of the lowestexplosive limit in air for these VOCs. Dimensions of the foam duringaging vary depending on the extrusion and aging conditions and theprecise composition of the resin from which the foam is made. The foammay expand or contract, although usually less than for an all VOCblowing agent. Typically, if expanding, the foam may expand from theas-extruded dimensions by as little as 5% and typically by 8% or less.Tight roll conditions that may inhibit aging and can damage the foamthrough compression during storage are avoided.

[0025] Expandable resin compositions for producing extruded polyolefinfoam products in accordance with the invention include a plasticizedpolyolefin resin mixed with a blended blowing agent as described. Theexpandable composition also normally contains a fatty ester aging ordiffusivity modifier and a nucleation agent for controlling the size ofthe cells of the foam. Aging modifiers are thought to have a minimalimpact on the diffusivity of carbon dioxide out of the cells of thefoam. The presence of small amounts of carbon dioxide in the blowingagent, in accordance with the invention, tends to preclude tightness inthe roll stock that is produced

[0026] In more specific detail, the expandable composition may include apolyethylene resin, about 0.5 to 5 kilograms of glycerol monostearateper 100 kilograms of the resin, about 0.05 to 0.5 kilograms of zincoxide per 100 kilograms of the resin, and about 1 to 20 kilograms ofblowing agent per 100 kilograms of the resin, which blowing agent has arelatively low percentage of carbon dioxide mixed with either normalbutane, isobutane, propane, or mixtures thereof.

[0027] Thus, a blowing agent of small amounts of CO₂ mixed with ethane,or normal- or iso-butane or propane is provided that is capable ofproducing extruded, low density thin foam sheets at high extrusion ratescomparable to VOCs, but with less instability after expansion and fasteraging characteristics.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] Various processes and equipment for extrusion foaming ofthermoplastic resins have been used for many years. Generally, solidpellets of thermoplastic resin are fed through a hopper to a meltingzone in which the resin is melted, or plasticized, to form a flowablethermoplastic mass. The plasticized thermoplastic mass generally is thenmetered to a mixing zone where the thermoplastic mass is thoroughlymixed with a blowing agent under pressure for subsequent cooling andexpansion of the resin to form a foam. Blowing agent typically isinjected between the metering and the mixing zones. The mixture ofthermoplastic resin and blowing agent is then forced through a die,which imparts a shape to the thermoplastic mass, into a zone of lowerpressure, such as atmospheric pressure. The blowing agent expands toform the cells of the foam and the thermoplastic foam is cooled.

[0029] Typical of much of the equipment used for extrusion ofthermoplastic foams, the thermoplastic pellets are conveyed from ahopper through the melt zone, the mixing and cooling zones, and extrudedthrough the die by a screw type apparatus. Single screw extruders arecommon, although double screw extruders sometimes are used for greatermixing.

[0030] When a blowing agent is injected into the mixing zone of thescrew extruder, the blowing agent initially forms a dispersion ofinsoluble bubbles within the plasticized thermoplastic mass. Thesebubbles eventually dissolve in the thermoplastic mass as the mixingcontinues and the pressure increases down the length of the extruder.The extruder should have a length to diameter ratio of at least 30:1 anda sufficient length of mixing zone to ensure that proper mixing occurs.

[0031] Thermoplastic resins contemplated for use in the practice of theinvention claimed herein include the polyolefin resins. Polyolefinresins may be defined as polymers derived from unsaturated hydrocarbonscontaining the ethylene or diene functional groups. Polyolefin resinsmay include virtually all of the addition polymers, however, the termpolyolefin typically is used for polymers of ethylene, the alkylderivatives of ethylene (the alpha-olefins), and the dienes. Among themore commercially important polyolefins are polyethylene, polypropylene,polybutene, and their copolymers. Polyethylene resins are particularlyuseful in the practice of the invention claimed herein.

[0032] Polyethylene is a whitish, translucent polymer of moderatestrength and high toughness. Polyethylene is available in forms rangingin crystallinity from 50 to 95 percent. Polyethylene is available inlow, medium, and high density polymer forms. For the low densitymaterial, the softening temperature is about 105° C. to 115° C. For thehigh density material the softening temperature is some 25° C. to 40° C.higher, or from about 130° C. to 140° C. Low, medium, and high densitypolyethylenes are suitable for extrusion foaming, including mixturesthereof.

[0033] The thermoplastic resin should be maintained at a temperaturewithin a range above the melting point of the polymer that issufficiently high so that the polymer has sufficient fluidity for mixingwith blowing agent. This range normally will be from about 20° C. to100° C. above the melting point of the resin. The melting zone can bemaintained at a somewhat lower temperature due to the heat that isgenerated by friction as the plasticized resin flows through theextruder.

[0034] After mixing, the temperature of the mixture of resin and blowingagent should be lowered closer to the melting point of the mixture sothat the polymer maintains its structure upon foaming, but not so muchthat complete expansion is hindered. The blowing agent has aplasticizing effect on the resin reducing its viscosity, or resistanceto flow, and so the melting point of the mixture of resin and blowingagent normally is below that of the resin alone. The expansiontemperature, which is above the melting point of the mixture, isempirically determined and depends upon the composition of the resin,the length of the screw, whether single or double screws are used, onthe specific resin, upon the amount of blowing agent, and the specificblowing agent blend. For a low density polyethylene, the expansiontemperature will generally be in the range of from about 85° C. to 120°C.

[0035] Additional general information on the production of polyolefinand other foams is available in the text Foam Extrusion, edited andcontributed to by Shau-Tarng Lee, Ph.D, and published in July 2000 byTechnomics, Lancaster, Pa., which is incorporated herein by reference inits entirety for the purpose of its general teachings.

[0036] The blowing agent contemplated for use in practicing theinvention claimed herein comprises a mixture of carbon dioxide andeither ethane, normal butane, isobutane, propane or mixtures of any twoor all of these hydrocarbons. Carbon dioxide should be present in anamount by weight of the blowing agent of about 25% by weight or less.Mixtures of 1%, 10%, 15%, 20%, and 25% carbon dioxide by weight and thebalance of either ethane, normal butane, isobutane, propane, or mixturesthereof are considered useful. The blowing agent is mixed into theplasticized polyethylene polymer resin in proportions to achieve thedesired degree of expansion in the resulting foamed cellular product.Stable foam densities from about 60 kg/m³ down to as low as 10 to 20kg/m³ may be made by practice of the invention and receive the benefitsof faster aging and greater dimensionally stability for facilitatingaging time. Typically, foams of from 20 to 25 kg/m³ are produced.

[0037] The blowing agent generally is mixed with the resin in a ratio ofabout one part blowing agent to ten parts resin. The maximum usefulproportion of blowing agent in the plasticized resin is affected by thepressure that is maintained on the resin in the extrusion die passage.

[0038] The benefits of using the blowing agent blend of the inventionclaimed herein may be enhanced by using a combination of a nucleationagent and an aging modifier to control cell size and development and tocontrol the replacement of blowing agent with air in the cells of thefoam, respectively. In particular, it has been found that a combinationof low levels of zinc oxide nucleation agent and glycerol monostearateaging modifier is useful to further reduce the density of the foamsproduced and results in a thickness increase.

[0039] The glycerol monostearate is mixed with the polyethylene resinprior to melting in an amount sufficient to produce a desirable rate ofexchange of air with blowing agent in the cells of the foam. Morespecifically, the glycerol monostearate is mixed with the polyethyleneresin prior to melting in an amount from about 0.5 to 5 kg per 100 kg ofpolyolefin resin. Still more specifically, glycerol monostearate isadded in an amount of 1 kg per 100 kg of polyolefin resin.

[0040] Zinc oxide nucleation agent is mixed with the resin in an amountsufficient to promote nucleation and to develop a pore structure of thedesired size. More specifically, zinc oxide nucleation agent is mixedwith the resin in an amount of from about 0.05 to 0.5 kg per 100 kg ofpolyolefin resin. Still more specifically, zinc oxide is added to theresin in an amount of 0.1 kg per 100 kg of polyolefin resin.

[0041] The foam is produced by continuously extruding the plasticizedresin and blowing agent mixture through a forming die and then rollingthe foam sheet into a roll for storage and aging. Extrusion rates inaccordance with the invention are above 100 kg/hr. Generally, rates of150 to 225 kg/hr are typical, but rates of 300 to 500 kg/hr can beachieved with large extruder diameters.

[0042] Aging is accomplished as the blowing agent gradually diffuses outof the cells of the foam and is replaced by air. Generally speaking, ifa blowing agent escapes too fast at a high temperature, then the foammay collapse and may not recover. If a flammable blowing agent does notescape fast enough, then the foam may require an uneconomical agingperiod or may pose a hazard, especially if stored in a confined area,such as a truck trailer.

[0043] Aging of foams is often expressed as a percentage of the lowestexplosive limit in air for the compound of interest. The lowestexplosive limit, or “LEL” is that lowest limit at which a concentrationof a particular VOC is explosive in air on application of a spark. Thehighest explosive limit is similar. However, at levels above the highestexplosive limit, the danger of fire or explosion is reduced since theconcentration of oxygenated air is reduced by the amount of hydrocarbonand the danger of explosive ignition is therefor also reduced. Normally,it is desirable to achieve no more than 70 to 80% of the LEL for aparticular VOC prior to shipment of a foam. Preferably, the foam is agedto less than 50% of the LEL for the blowing agent. Propane foamstypically take about 6 days to age properly.

[0044] The following Tables 1 through 3 compare the results achievedusing examples of blowing agent according to the invention to examplesbased on a blowing agent of 100% propane for production of thin sheetsof extruded low density polyethylene foam, as set forth above. In eachof Tables 1 through 3, the foam sheet is measured in the thicknessdimension in inches at the time the foam is produced and thereafter atthe time intervals indicated.

[0045] As can be seen in Table 1, the samples produced with 100% propaneblowing agent increased in thickness from the time they were firstextruded by about 17% to their maximum dimension. In contrast, the foamproduced with about 15% CO₂ in the blowing agent by weight increased inthickness by less than 8%. Tables 2 and 3 show similar results for afoam produced from 100% propane. However, the foams produced with ablowing agent having 20% CO₂ in the blend (Table 2) and having 15% CO₂and 25% CO₂ in the blend (both in Table 3) initially collapsed a smalldegree of from about 1% (Table 3) to as much as 14% (Table 2), but thenrecovered their volume. Collapse normally is not considered desirable,but these foams recover, are of good quality, age quickly, and avoidproducing tight roll stock that can block the pathway for exchange ofair and VOC and can damage the roll stock. Too tight a roll compressesthe inner layers and can result in machine direction thicknessvariations.

[0046] The foam produced with 100% propane blowing agent expandssufficiently to impact the path for exchange of blowing agent with air.In contrast, the roll stock produced in accordance with the inventionremains sufficiently loose to promote exchange of blowing agent withair, which increases the speed by which the foam can be aged. TABLE 1Blowing Agent 100% 85% Propane/ Propane 15% CO₂ Sample 1 2 3 4 Hotinitial foam .053 .058 .064 .056 thickness, inches  1 minute .055 .060.064 .056  2 .056 .061 .064 .056  3 .056 .061 .065 .056  4 .057 .062.065 .056  5 .057 .063 .065 .056 10 .059 .065 .065 .056 Every 15 minutes.060 .066 .067 .058 30 .062 .068 .068 .059 45 .060 .068 .068 .057 1 hour.060 .067 .069 .056 1:15 .060 .067 .066 .056 1:30 .058 .066 .066 .0551:45 .058 .067 .065 .055 2 hours .057 .067 .064 .052 2:15 .057 .066 .064.053 2:30 .056 .066 .062 .053 2:45 .055 .064 .062 .052 3 hours .054 .063.061 .053 3:15 .054 .063 .061 .052 3:30 .055 .063 .060 .051 3:45 .053.062 .060 .051 4 hours .055 .060 .061 .052 4:15 .052 .059 .060 .052 4:30.059 .052 4:45 .060 .053

[0047] TABLE 2 Blowing Agent 100% 80% Propane/ Propane 20% CO₂ Sample 12 3 4  1 minute thickness, .132 .127 .128 .129 inches  2 .135 .129 .123.126  3 .137 .131 .122 .125  4 .138 .134 .120 .124  5 .140 .136 .119.122 10 .143 .138 .117 .120 Every 15 minutes .145 .140 .113 .117 30 .145.140 .110 .115 45 .148 .143 .112 .114 1 hour .147 .141 .117 .116 1:15.146 .142 .123 .121 1:30 .146 .140 .123 .123 1:45 .148 .145 .124 .123 2hours .147 .141 .130 .127

[0048] TABLE 3 Blowing Agent 85% propane/ 75% Propane/ 100% Propane 15%CO₂ 25% CO₂ Sample Hot Initial .128 .131 .130 Thickness, inches  1minute .127 .130 .128  2 .126 .129 .126  3 .126 .128 .124  4 .126 .128.123  5 .126 .129 .122 10 .130 .130 .121 15 .133 .131 .120

[0049] Table 4, below, shows the aging characteristics for the foam ofthe invention compared to foams produced with a 100% propane blowingagent. The data for foam produced with 100% propane blowing agent wasobtained after 6 days. The data for the foam produced with 15% CO₂ inthe blowing agent (the remainder was propane) could be obtained afteronly 3 days.

[0050] Rolls of freshly extruded foam roll stock produced with each ofthe blowing agents were placed in separate closed trailers for storageand aging. Temperature, wind, and humidity conditions were monitored.The readings were obtained from the center of the trailer about 6 inchesoff the bottom, since the VOCs are heavier than air and tend to becomeconcentrated there. The numbers shown are for the percentage of thelowest explosive limit reached at each particular time. Generally, it isdesirable to be below about 70% of the lowest explosive limit of a VOCin air.

[0051] In all cases, the foams produced with blowing agent of theinvention showed comparable aging in half the time of foams producedwith a 100% propane blowing agent. TABLE 4 Time inside trailer 3 Day CO₂6 Day Propane Day 1 - 8:00 am 5% 4% Day 1 - 4:00 pm 6% 5% Day 2 - 8:00am 2% 2% Day 2 - 4:00 pm 7% 4% Day 2 - 12:00 am 6% 3% Day 3 - 9:30 am 1%4% Day 5 - 8:30 am — 1% Day 5 - 5:30 pm 2% 2% Day 5 - 12:35 am — 1% Day6 - 7:30 am — 1% Day 6 - 5:00 pm — 1% Day 6 - 12:40 am 1% — Day 7 - 8:00am — 1%

[0052] The invention has been described in particular embodiments. Theseembodiments should be considered illustrative of and not in limitationof the invention described herein. The full scope of the inventionshould be judged in accordance with the appended claims and equivalentsthereto.

What is claimed is:
 1. A blowing agent blend for producing continuouslyextruded polyolefin foams comprising carbon dioxide present in an amountof from about 1 to less than 20% by weight of the blowing agent, thebalance of the blowing agent composition being selected from the groupof hydrocarbons consisting of ethane, propane, normal butane, isobutane,and mixtures of any two or more thereof.
 2. An extrudable, expandablecomposition for producing stable, low density polyolefin foam products,said composition comprising: a) a plasticized polyolefin resin; b) anaging modifier present in an amount sufficient to control shrinkage ofthe foam; and c) a blowing agent for expanding the compositioncomprising carbon dioxide and a hydrocarbon selected from the groupconsisting of n-butane, isobutane, propane, and mixtures thereof, saidcarbon dioxide being present in an amount by weight of from 1 to lessthan 20% by weight of the blowing agent.
 3. The expandable compositionof claim 2 wherein said polyolefin resin includes a nucleation agentpresent in an amount sufficient to promote a uniform pore structure. 4.The expandable composition of claim 2 wherein said polyolefin resinincludes an aging modifier present in an amount of from about 0.5 to 5kg per 100 kg of resin, a nucleation agent present in an amount of fromabout 0.05 to 0.5 kg per 100 kg of resin, and wherein said blowing agentis present in an amount of from about 1 to 20 kg per 100 kg of resin. 5.The expandable composition of claim 2 wherein said polyolefin resin is apolyethylene resin and includes glycerol monostearate and talc.
 6. Theexpandable composition of claim 2 wherein said blowing agent comprisescarbon dioxide and a hydrocarbon selected from among the groupconsisting of n-butane, isobutane, propane, and mixtures thereof, andwherein said carbon dioxide is present in said blowing agent in anamount of about 10% by weight.
 7. An expandable composition forproducing polyethylene foam products, said composition comprising: a) aplasticized polyethylene resin; b) an aging modifier in an amount offrom about 0.5 to 5 kg per 100 kg of resin; c) a nucleation agent in anamount of from about 0.05 to 0.5 kg per 100 kg of resin; and d) ablowing agent in an amount of from about 1 kg to 20 kg per 100 kg ofresin for expanding the composition, said blowing agent comprising ablend of about 10% to 15% by weight of carbon dioxide, the balance beinga hydrocarbon selected from the group consisting of n-butane, isobutane,propane, and mixtures thereof.